Patent GB-731114-A (GB)
Title: Improvements relating to metal-containing azo dyestuffs and their use
IPC: C09B45/14
Filed: 1953-04-07
Abstract: The invention comprises dyes of the formula D-M-D1, where M represents chromium or cobalt, D is a co-ordinated monoazo dye containing no acid water-solubilizing groups of the formula <FORM:0731114/IV (c)/1> where A is a radical of the benzene series containing the OH ortho to azo, B is a radical of a coupling component containing the OH ortho to azo, Y is -CO-, -SO2-, or -SO2NR- (R being alkyl of 1-3 carbon atoms), Z is a radical of the benzene series, and n is 1 or 2, and D1 is the same as D or is another co-ordinated O,O1-dihydroxy monoazo dyestuff containing no acid water-solubilizing groups. They are made by metallizing in substance or on wool or similar fibres the dyestuffs of the above formula, or corresponding dyestuffs in which the OH attached to A is alkoxy, alone or in equimolecular admixture with another O,O1-dihydroxyazo-dyestuff having no acid water solubilizing groups. The dyestuffs dye silk, casein fibres, nylon, and superpolyurethane fibres.  In examples, 2-amino-1-phenol-4-phenylsulphone-31-sulphonamide is diazotized and coupled with (1) 1 - acetylamino - 7 - hydroxynaphthalene; (2) 1 - carbomethoxyamino - 7 - hydroxynaphthalene; (3) 7-hydroxynaphthyl-(1)-carbamic acid methoxyethyl ester; (4) 1-phenyl-3-methyl - 5 - pyrazolone; (5) a mixture of 1 - carbomethoxyamino - 7 - hydroxynaphthalene and 1 - (31 - chlorphenyl - 3 - methyl - 5 - pyrazolone, followed by chroming with ammonium chromo-salicylate, or with (6) 1-(31-chlorophenyl - 3 - methyl - 5 - pyrazolone; or (7) 2-hydroxynaphthalene, followed by cobalting with cobalt acetate; cobalting may also follow (5) above.  Also in examples, the following dyestuffs are chromed: (8) 4-chloro-2-aminophenol --> 1-naphthol-5-sulpho-N-ethyl-N-phenylamide-31-sulphonamide; (9) 6-nitro-4-methyl - 2 - aminophenol --> 1 - (311 - sulphonamido - 31 - phenylsulphonylphenyl) - 3 - methyl-5-pyrazolone; (10) 2-aminophenol-4-sulpho-N-ethyl - N - phenylamide - 41 - sulphonamide --> 1 - (31 - chlorphenyl) - 3 - methyl - 5 - pyrazolone; (11) 2-aminophenol-4-phenylketo-31-sulphonamide --> acetoacetic anilide. Also in examples: (12) a mixture of diazonium chlorides from 2 - aminophenol - 4 - phenylsulphone - 31 - sulphonamide and 2-aminophenol-4-methylsulphone is coupled with 2-hydroxynaphthalene, followed by cobalting as above.  A dyeing example on wool is given and a number of other starting materials are referred to, which have been made from, e.g., 2,4-dihydroxyquinoline as coupling component.ALSO:3 - Nitro - 1,11 - diphenylsulphone - 31 - sulphonamide and its 4-chloro derivative are made from the 3-nitro-1,11-diphenylsulphone by sulphonation, and reaction first with phosphorus pentachloride and then with ammonia.  The 3-nitro group may be reduced to give 3-amino-1,11 - diphenylsulphone - 31 - sulphonamide which is diazotized and reduced to give the 3-hydrazino body, which is reacted with acetoacetic ester to give the 3-pyrazolonyl derivative.  The 4-chloro-3-nitro - 1,11 - diphenylsulphone - 31 - sulphonamide is converted to the 4-hydroxy body with alkali, and the nitro group is reduced to amino.  1 - Naphthol - 5 - sulpho - N - ethyl - N-phenylamide - 31 - sulphonamide is obtained from 1-naphthol-5-sulphonic acid and N-ethylaniline-3-sulphonic acid by customary methods, with temporary esterification of the hydroxy group with p-toluenesulphochloride.  2 - Amino - 1 - phenol - 4 - sulpho - N - ethyl-N - phenylamide - 41 - sulphonamide is produced from N-ethylaniline-4-sulphonic acid and 1 - chloro - 2 - nitrobenzene - 4 - sulphochloride with conversion of the sulphonic group, exchange of chlorine for hydroxy, and reduction of the nitro group.  2 - Amino - 1 - phenol - 4 - phenylketo - 31-sulphonamide is obtained from 1-chloro-2-nitrobenzene-4-phenylketone by sulphonation, conversion of sulpho to sulphonamide, chlorine to hydroxy, and nitro to amino.